In-situ surfactant and chemical oxidant flushing for complete remediation of contaminants and methods of using same

ABSTRACT

The present invention relates to the removal of subsurface contaminants and methods of using same. In more particular, but not by way of limitation, the present invention relates to an integrated method for remediating subsurface contaminants through the use of a low concentration surfactant solution (and methods of making and using novel surfactant solutions) followed by an abiotic polishing process to thereafter achieve a substantially reduced subsurface contaminant concentration that surfactant flushing alone cannot achieve. The present invention is focused on remediation of high viscosity hydrocarbons, such as heating oils or coal tars, with a combination of pre-injection of bio-co-solvent and surfactant (and polymer) flush approach.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. Ser. No. 11/594,488 filed Nov. 8, 2006 now abandoned, which is a continuation-in-part of U.S. Ser. No. 11/054,582, filed Feb. 9, 2005, now abandoned; which is a continuation of U.S. Ser. No. 10/290,424, filed Nov. 6, 2002, now U.S. Pat. No. 6,913,419; which claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Application Ser. No. 60/333,244, filed Nov. 6, 2001, entitled “USE OF IN-SITU SEQUENT AND CHEMICAL OXIDANT FLUSHING FOR COMPLETE REMEDIATION OF CONTAMINATED SOILS AND GROUNDWATERS”, the contents of which are expressly incorporated herein in their entirety by reference.

BACKGROUND OF INVENTION

1. Field of the Invention

The present invention relates to the removal of subsurface contaminants and methods of using same, and more particularly, but not by way of limitation, the presently claimed and disclosed invention(s) relate to an integrated method for remediating subsurface contaminants through the use of a low concentration surfactant solution (and methods of making and using novel surfactant solutions) followed by an abiotic polishing process to thereafter achieve a substantially reduced subsurface contaminant concentration that surfactant flushing alone cannot achieve. Additionally, the surfactant solution alone can be used to achieve a substantially reduced subsurface contaminant concentration. Finally, the presently claimed and disclosed invention(s) include the use of a biodegradable co-solvent capable of substantially reducing subsurface contaminants having a viscosity of from 50-1500 cp and/or a low aqueous solubility.

2. Background Information Relating to the Invention

Surfactant enhanced subsurface remediation (SESR) is a unique technology for expediting subsurface remediation of non-aqueous phase liquids (NAPLs). Studies known to those in the art have previously evaluated the SESR technology in both laboratory scale studies and field scale demonstration studies. Traditionally, the surfactant system in SESR (typically an anionic or nonionic surfactant), is designed to remove organic contaminants (including chlorinated solvents) from contaminated soil. Surfactant systems significantly increase the solubility of hydrophobic organic compounds and, if properly designed and controlled, also significantly increase the mobility of NAPLS. A significantly reduced remediation time thereby results, as well as increased removal efficiency (up to 3 or 4 orders of magnitude) and reduced cost of NAPL removal through use of surfactant system for subsurface remediation.

Surfactant flushing solutions, typically, can be designed to be effective under most subsurface conditions. In most cases, the effectiveness of the surfactant flushing solutions is not reduced due to the presence of more than one contaminant. Naturally-occurring divalent cations and salts may affect the performance of certain surfactants, as well as the removal efficiency for cationic heavy metals. It is possible, however, to design an effective surfactant system for removal of the target contaminants under any of these conditions. A number of factors influence the overall performance and cost effectiveness of SESR systems. These factors include: local ground water chemistry; soil chemistry (e.g. sorption, precipitation); ability to deliver the surfactant solution to the area of contamination; surfactant effects on biodegradation of the NAPL compounds as well as degradation of the surfactants; public and regulatory acceptance; cost of the surfactant; recycle and reuse of the surfactant, if necessary; and treatment and disposal of waste streams. Bench scale tests (treatability studies) must be conducted on site specific soils and NAPL (if available) to ensure the optimal system is selected for a particular site.

Surfactant flushing can remove a large portion of the mass of subsurface contaminant liquid. In general, it is not expected that surfactant flushing alone will have a high probability of reducing the subsurface contaminant concentration to a level necessary to allow the site to be considered “remediated.” Therefore, a treatment train (or integrated) approach is necessary to speed up or achieve the closure of the site. It is to such an integrated approach involving a pre-selected surfactant solution flush coupled with an abiotic oxidation polishing step and methods thereof that the presently disclosed and claimed invention(s) is directed.

Typically, the viscosities of contaminants or NAPLs are between one to ten centipoises (cp, or 10⁻² g cm⁻¹sec⁻¹) and, in some occasions, they may reach tens up to one hundred centipoises. Prior art (crude) oil recovery industries that used surfactant flushing for removal of highly viscous oils would generally apply a polymer solution (or so called “polymer drive”) in order to increase the sweep efficiency and oil recovery from the porous media and/or soils. Other generally known methods involve the addition of heat to reduce the oil viscosity, or the injection of foam in order to gain better mobility control to achieve higher oil recovery.

Such generally known methods are limited with respect to recovering significant amounts of complex viscous liquid contaminants, such as coal tars (commonly found at former manufactured gas plants), heating oils, bunker oils, creosotes (used as wood preservatives), polychlorinated biphenyls (PCBs), dioxins, and motor oils. Some of these complex waste oils might contain tens to hundreds of different compounds. Unfortunately, these complex wastes found at contaminated sites could also sometimes reach viscosities of from 50 to 1500 cp. In addition to these high viscosities, the low aqueous solubility of these complex organic fluids also poses a significant challenge for any attempt to remediate the impacted soil and groundwater.

Therefore, an improved surfactant flushing system is herein claimed and disclosed that is capable of substantially reducing the subsurface contamination of complex viscous NAPLS.

SUMMARY OF THE PRESENT INVENTION

The present invention is directed to a method for substantially removing subsurface contaminants through an integrated approach utilizing a pre-selected surfactant solution and a pre-selected chemical oxidant. Such an innovative integrated approach satisfies a need in the marketplace for a cost-effective and less time consuming system to remove substantially all subsurface contaminants—a level of remediation that has been traditionally unavailable. A method of the present invention comprises the steps of introducing an effective amount of at least one pre-selected surfactant solution and an effective amount of at least one pre-selected chemical oxidant. The combination of the pre-selected surfactant solution and the pre-selected chemical oxidant are capable of substantially removing subsurface contaminants. Additionally, the surfactant solution alone can be used to achieve a substantially reduced subsurface contaminant concentration. Finally, the presently claimed and disclosed invention(s) include the use of a biodegradable co-solvent capable of substantially reducing subsurface contaminants having a viscosity of from 50-1500 cp and/or a low aqueous solubility, which will be difficult to remove using the patented surfactant system-alone as documented in the previous claim.

The presently claimed and disclosed invention(s) also relate to a subsurface contaminated site that is substantially remediated by this integrated approach and novel surfactant solutions.

DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 is a schematic diagram showing, generally, an integrated surfactant flushing and treatment system according to the present invention.

FIG. 2 is a graphical representation showing the results of a NAPL removal test in a one-dimensional (1-D) column.

FIG. 3 is a schematic representation of pre- and post-surfactant free phase gasoline distribution in a “Shallow Zone” at an underground storage tank contamination site—i.e. Carroll's Grocery in Golden, Okla.

FIG. 4 is a schematic representation of pre- and post-surfactant flushing/chemical oxidation benzene concentration distribution methodology of the present invention in a “Shallow Zone” at an underground storage tank contamination site—i.e. Carroll's Grocery in Golden, Okla.

FIG. 5 is a graphical representation showing the results of a TCE breakthrough test with sequent surfactant and chemical oxidation flushing in a 1-D column.

DETAILED DESCRIPTION OF INVENTION

It is to be understood that the invention is not limited in its application to the details of construction and the arrangements of the components set forth in the following description (e.g. texts, examples, data and/or tables) or illustrated or shown in the drawings. The invention is capable of other embodiments or of being practiced or carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein is for purpose of description and should not be regarded as limiting and one of ordinary skill in the art, given the present specification, would be capable of making and using the presently claimed and disclosed invention in a broad and non-limiting manner.

As used herein, the term “subsurface contaminant” refers to any organic or inorganic impurity or halogenated solvent (such as a chlorinated solvent) that is toxic to the underground surface. Additionally, the term “surfactant solution” refers to any anionic or nonionic surfactant or co-surfactant combination that is functionally capable of removing organic or inorganic contaminants as well as halogenated solvents (such as a chlorinated solvent) from a contaminated subsurface area, such as subsurface soil or water systems. Further, the term “oxidant” refers to any oxidizing agent capable of degrading a contaminated plume or entrapped residual pollutants whether they are organic, inorganic, or halogenated solvents. The term “polishing step” as used herein, refers to the innovative abiotic process of the presently disclosed and claimed invention that includes the steps of injecting or introducing predetermined concentrations of a chemical oxidant to further degrade and reduce the subsurface contaminant subsequent to a surfactant flushing step. “Integrated approach” as used herein, refers to a low concentration surfactant flush in combination with the abiotic polishing step. “Remediation” as used herein, refers to the substantially complete removal of soil and groundwater pollutants by various treatments or restoring methods to achieve the standard set by the responsible regulatory agency for the particular contaminated subsurface system (e.g. National Primary Drinking Water Regulations (NPDWR) for subsurface ground water).

Due to certain advantages associated with the use of the integrated approach of the presently claimed and disclosed invention, one of ordinary skill in the art will most likely recognize the benefits of this approach when time is of the essence. One such advantage is that by using the low concentration surfactant flush step in combination with the subsequent abiotic polishing step, a higher probability exists of reducing the subsurface contaminant concentration to a level necessary to allow the site to be considered remediated—i.e. substantially all contaminants have been removed. This process will tend to achieve minimal pollutant content of the underground surface while decreasing the time spent as compared to prior art techniques that utilize a higher concentration surfactant flush as the sole means of remediating a contaminated site.

Prior to the inventive concept of the present invention, higher concentration surfactant flushing alone has been the common method of site remediation. As shown in FIG. 1, the present invention includes an overall integrated surfactant flushing and treatment system 10. A pre-determined surfactant solution 20 is prepared in a mixing tank 30. After the surfactant solution 20 is prepared, the surfactant-NAPL phase behavior is evaluated on-site. If the surfactant solution 20 meets all criteria set for the surfactant—NAPL phase behavior, such as optimal microemulsion (either Winsor Type III or Type I), the surfactant solution 20 is delivered to a targeted treatment zone 40 via an injection well 50 and a pumping system 60. Removed contaminant and surfactant solution 70 is extracted from a recovery well 80. The free-phase oil is separated from a surfactant stream in an oil/water separator 90. If the contaminant and surfactant solution 70 is pH sensitive for its recovery, a pH-adjustment tank 100 could be added before the oil/water separator 90 to reduce the solution pH and enhance the surfactant separation. From the oil/water separator 90, a waste stream 110 is sent to an air stripper 120 or other equipment (such as liquid-liquid extraction) to remove dissolved volatile organic chemicals (VOC) 130. The waste stream 110 is delivered to a pre-filtration system 140 to remove the large solid particle or sediment in the waste stream 110. If surfactant reuse is required, the waste stream 110 will go through a second pH-adjustment tank 150 and an ultrafiltration membrane system 160. Most surfactant micelle phase will be rejected at the retentate side 170 and sent back to the mixing tank 30 for reuse. The waste water containing mainly surfactant monomer and trace contaminant will pass through the ultrafiltration membrane system 160 for final disposal 180 or sent to a wastewater treatment plant for treatment.

As outlined and shown in particular examples hereinafter, the presently claimed and disclosed methodology of the present invention demonstrates significant removal of NAPL from a contaminated source area via remediation. In one embodiment of this invention, surfactant flushing projects were conducted at a surfactant concentration ranging between 3 to 8 wt % of surfactant based upon the total weight of the surfactant solution (e.g. 3 wt % would be 3% surfactant/97% water or other solvent). This range may be somewhat over-conservative because, within this range of surfactant concentrations, reuse or reconcentration of the recovered surfactant typically is necessary to improve the economics of the overall project. In order to recover/separate the surfactant, contaminant concentrations must be reduced to acceptable levels in the surfactant solution and then the surfactant must be re-concentrated for reinjection. In other embodiments of this invention, surfactant concentrations in a range from about, 0.05% to about 15 wt % are contemplated for use. In a most preferred embodiment of this invention, a lower surfactant concentration, such as 0.1%, is most desirable. Several advantages of using a low surfactant concentration, are: (1) significant savings on chemical use and project cost; (2) minimizing and/or completely eliminating the reuse and recycling of the recovered surfactant; and (3) improving the above-ground treatment efficiency (e.g., less retention time for breaking the macro- or microemulsion during the oil/water separation stage, and less foaming of surfactant). Therefore, the ability of lowering the costs of a SESR project, such as with utilizing a lower surfactant concentration, further improves the total cost effectiveness for the remediation of sites. The quantity of surfactant necessary for use with the presently disclosed and claimed invention is up to one order of magnitude (from several weight percents reduced to several thousands ppm or mg/L) less than prior art surfactant flushing systems used for light non-aqueous phase liquids (LNAPLS) as well as for dense non-aqueous phase liquids (DNAPLs).

The surfactant solution of the presently claimed and disclosed invention may be any anionic, cationic, or nonionic surfactant or any combinations thereof as well as one or more combinations thereof. These combinations include, but are not limited to: anionic surfactant/anionic surfactant; anionic surfactant/nonionic surfactant; anionic surfactant/cationic surfactant; nonionic surfactant/nonionic surfactant; and nonionic surfactant/cationic surfactant combinations, to name but a few of the possible permutations.

Further, the present invention encompasses an abiotic process to address the post-surfactant polishing step to further enhance site remediation. This abiotic process involves injecting pre-determined concentrations of chemical oxidant to degrade the dilute contaminant plume and/or trace entrapped residual pollutant(s) that remain after the surfactant flushing step. The effectiveness of these oxidants depends on the types of contaminants and geological formations found at the site. Thus, the chemical oxidant is chosen or “predetermined” based on an analysis of the site: i.e. the functionality of the chemical oxidant must match or be capable of degrading any remaining contaminants or pollutants. Thus, one of ordinary skill in the art, given the present specification, would be capable of selecting an appropriate chemical oxidant given an identification of the contaminants or pollutants to be remediated.

The two most common oxidizing agents used for in-situ chemical oxidation are hydrogen peroxide and potassium permanganate, yet various other oxidizing agents including, but not limited to, sodium permanganate, ozone, chlorine dioxide, or dissolved oxygen may be used. In the chemical oxidation process known as Fenton's reaction, injection of hydrogen peroxide is typically combined with an iron catalyst under reduced pH conditions to generate powerful hydroxyl free radicals (OH.). Since 1934, Fenton's reagent has been recognized as an effective means for destroying organic compounds in wastewater and most recently as an in-situ treatment method for soil and groundwater. The dissolved iron acts as a catalyst for generating the hydroxyl radical, resulting in free-radical oxidation of the contaminant. A low pH is necessary to keep the iron in the ferrous state. While the reaction can be performed successfully at a pH range between 5 and 7 (using a so-called modified Fenton's Reagent and processes), the performance improves at even lower pH values (as low as 2 to 3). Obtaining optimal subsurface pH conditions is often limited by the soil buffering capacity, which is site-specific. For example, if naturally-occurring carbonates in the soil are high, a significant acid dose is required to reduce the pH at the site and thereby improve the performance of the oxidizing agent.

Potassium permanganate oxidation creates little heat or gas, therefore contaminant treatment occurs primarily through oxidation. Potassium permanganate is an oxidizing agent with a unique affinity for organic compounds containing carbon-carbon double bonds, aldehyde groups or hydroxyl groups. Under normal subsurface pH and temperature conditions, the primary oxidation reaction for perchloroethylene (PCE) and trichloroethylene (TCE) involves spontaneous cleavage of the carbon-carbon bond. Once this double bond is broken, the highly unstable carbonyl groups are immediately converted to carbon dioxide through either hydrolysis or further oxidation by the permanganate ion. Selection of the proper oxidant is based on several factors including, but not limited to, contaminant characteristics, site geochemical conditions, soil buffering conditions of site, and etc. Fenton's reagent is capable of oxidizing a wide range of compounds while potassium permanganate is more selective and is best suited for chlorinated ethene contaminants such as PCE and TCE. Potassium permanganate often provides more rapid destruction of specific compounds when compared to Fenton's reagent, however.

Previous prior art results from field tests raised concerns on the effectiveness of using chemical oxidation for contaminated source zone remediation. Mainly, this was due to the high concentration of oxidant required, the large amount of heat and gas released in the subsurface, and the formation of solid-precipitate at the surface of the contaminant liquid pool. Utilizing the presently disclosed and claimed methodology, however, the bulk of the contaminant has been previously removed by surfactant flushing, followed by a very low concentration (preferably less than 1.0 wt %) of oxidant which can be used. The amount of heat generated and the volume of gas released ceases to be a limiting factor. Using the methodology of the presently claimed and disclosed invention, surfactant flushing followed by chemical oxidation is highly effective for contaminant remediation. Thus, neither surfactant flushing nor chemical oxidation alone can accomplish substantially, one hundred percent remediation of a contaminated site. The combination of surfactant flushing followed by chemical oxidation does, however, result in a substantially remediated site that had been contaminated prior to treatment. The presently disclosed and claimed methodology greatly reduces the long-term risk and financial burden of the owner of the contaminated site in a site closure program versus a maintenance-like approach such as pump-and-treat. The uniqueness of the presently claimed and disclosed integrated process approach provides significant improvement on the NAPL clean-up efficiency as compared to the stand-alone surfactant flushing and stand alone in situ chemical oxidation for site remediation.

Experiment Methodology

Surfactant Selection and System Design. Selection of the proper surfactant system utilizing a series of laboratory screening tests is one of the most crucial steps in conducting a successful surfactant flushing project. Laboratory surfactant screening typically consists of the following tests: contaminant solubilization tests, surfactant-NAPL phase behavior properties tests, surfactant sorption and precipitation tests, and contaminant extraction-column studies. Representative procedures of these tests are briefly described below. One of ordinary skill in the art, however, would appreciate the significance and steps necessary to conduct such tests given the present specification. The purpose of these tests is to select the best surfactant system for application at the site—the surfactant is optimized for both the physical and chemical conditions of the site and the contaminant.

Contaminant solubilization of NAPL Solubilization tests are used to determine the solubilization capacity of the surfactant systems (see e.g. Shiau et al., 1994; Rouse et al. 1993). For a DNAPL contaminant, the objective of the solubilization test is to select a surfactant system with ultra-solubilization potential without mobilizing the NAPL. For a LNAPL contaminant, the optimal surfactant system is chosen based on mobilization of NAPL under the ultra-low interfacial tension condition. Typically, surfactant systems under such conditions will produce a so-called Winsor Type III (or the middle phase) microemulsion via testing of surfactant-NAPL phase behavior properties (Shiau et al., 1994). The solubilization capacity of site-specific NAPL is determined for the surfactants by two methods: direct visual observation (see Shiau et al., 1994) and gas chromatography/flame ionization detector (GC/FID) (i.e., EPA Method 8015 for gasoline range organics (GRO), diesel range organics (DRO), and other volatile organic chemicals (VOCs)) and/or gas chromatography/photoionization detector (GC/PID) measurement (i.e., EPA Method 8021B for BTEX compounds). Direct visual observation is used as a preliminary screening tool for various surfactant and NAPL systems. When a proper surfactant/co-surfactant system is utilized, a middle-phase microemulsion (a translucent liquid phase intermediate between the water and NAPL phases) is observed in a mixture of surfactant and NAPL system.

Surfactant-NAPL phase behavior properties. The difference between a microemulsion and macroemulsion (or emulsion) is that a microemulsion is thermodynamically stable while a macroemulsion is thermodynamically unstable and will ultimately separate into oil and water phases. Typically, a macroemulsion of NAPL and surfactant mixture appears opaque after equilibration. During the surfactant-NAPL phase behavior testing, equal volume of NAPL and surfactant solution is added to a batch reactor (at capacity between 10 mL to 40 mL) and the system is adjusted with salt (NaCl), hardness (CaCl₂), or co-solvent (short chain alcohols) to change the hydrophobicity, a crucial parameter to achieve the optimal surfactant phase behavior, of NAPL and surfactant mixture. The solution is shaken and left to equilibrate at room temperature (18° C.) following a 24-hour pre-mixing period. Formation of a stable middle-phase microemulsion becomes complete within a few hours to one day. The presence of a middle-phase microemulsion is confirmed by visual observation (formation of a translucent liquid) and instrumentation (measuring the ultra-low interfacial tension (IFT) with a spinning drop tensiometer). (See Cayias et. al, 1975; Shiau et. al, 2000).

Sorption, Precipitation, and Phase Behavior Analyses. These tests assess the potential for surfactant losses under subsurface conditions (see Shiau et al., 1995 for details). Surfactants can be lost due to sorption, precipitation, and adverse phase behavior reactions. Excess surfactant sorbed or precipitated onto soil inhibits system effectiveness and increases costs. Sorption testing quantifies the amount of surfactant lost to soil and facilitates a surfactant comparison analysis. Some surfactants may precipitate or phase separate due to the presence of salts, divalent cations or temperature fluctuations. It is essential to ensure that the surfactant will not precipitate under site specific aquifer conditions. Surfactant loss due to precipitation and/or phase separation not only hinders performance but also plugs the aquifer. Formation of an opaque solution in a mixture of NAPL/surfactant indicates an adverse phase behavior, which does not provide a satisfactory sweep efficiency and/or solubilization capacity in the subsurface.

Contaminant Extraction-Column Studies. One-dimensional (1-D) column tests are conducted to simulate flow through conditions in the aquifer (see Shiau, et al., 2000 for detailed procedures). Although it is difficult to simulate actual site conditions, valuable information can be obtained from column studies. This information includes solubilization enhancement under continuous flow conditions and head losses during flushing through the media.

The results of the column studies aid in the design of pilot and potential full-scale application designs of the presently claimed and disclosed inventive methodology. Column test results are used to quantify the number of pore volumes (PV) required to mitigate the NAPL for each surfactant system and the polishing step. Previous laboratory and field studies indicate that the solubilization mechanism requires 3-15 PV for most NAPL mass recovery (Shiau, et al. 2000). For the mobilization mechanism, the required surfactant solution flush is between one to two pore volumes (PV) to recover the majority of the NAPL mass. From site soil-packed columns, residual saturation is achieved in the column by adding the site-specific contaminant(s) to the column (between 0.01 to 0.2 PV) followed by water to remove excess contaminant. A mass balance of NAPL is determined to estimate the residual concentration.

Under low surfactant concentration conditions (<1 wt % of surfactant), reuse and recycling of surfactant is economically unnecessary for full-scale implementation. Addition of bio-degradable co-solvent to the pre-selected surfactant solution for highly viscous contaminants as claimed and disclosed in this invention will increase the costs of chemical use and the remediation project. Therefore, recycled bio-co-solvent might be necessary to save the chemical and remediation costs. New processes may be developed for the recycling and reuse of the bio-degradable solvent. If injection of a higher concentration surfactant is necessary at the particular site, one of ordinary skill in the art could use membrane-based systems, such as Micellar Enhanced Ultrafiltration (MEUF), to recover and reuse the surfactant. (Lipe et al., 1996; Sabatini et al., 1998b.)

Chemical Oxidation as a Polishing Step. In the presently claimed and disclosed invention, surfactant flushing is followed by a polishing stage utilizing the introduction of a chemical oxidant to substantially degrade the contaminant left in the soil and groundwater subsequent to the surfactant flushing step. Bench-scale experiments are conducted to evaluate the effectiveness of in-situ chemical oxidation in order to illustrate and evaluate the primary performance characteristics of the technology, including (1) oxidant-contaminant reaction kinetics, (2) matrix interactions and other secondary geochemical effects, (3) subsurface oxidant transport, (4) overall oxidant consumption, and (5) contaminants treated and overall reductions achieved.

Chemical Oxidant Selection and System Design. The first step in the process of chemical oxidant polishing is selecting the proper oxidant for the site. The two most common oxidants used for process applications are hydrogen peroxide, or modified Fenton's Reagent (with a catalyst added under higher or neutral pH), which will be applied at the active petroleum gas station and/or active chemical plants to minimize the corrosion of the metal fittings and pipings, and potassium permanganate, however sodium permanganate, ozone, chlorine dioxide, dissolved oxygen or any other oxidant, in which a person having ordinary skill in the art may be familiar, may be tested and be used in this system. To ensure a successful project, several design steps of a chemical oxidation polishing system should be satisfied. An understanding of relative reaction rates and the life span of reactants are required to ensure adequate contact time for the desired reactions. The chemical demand associated with pH adjustment is evaluated since many of the oxidation reactions are pH-dependant. In addition, geochemical characteristics of the site are identified to help predict how naturally occurring mineral and organic fractions within the soil and ground water will affect the process.

Before installing a field-scale chemical oxidation system, certain data is be collected to ensure proper chemical addition ratios and reaction times are achieved at the site. This information may include, but is not limited to, data on the reaction kinetics, pH conditions, and naturally occurring interference within the subsurface for the specific site. In addition, mobility control and transport of the injected oxidant to the target areas is crucial, especially at a site with less of a permeability zone and having high organic and mineral interference.

Degradation Test. Similar to surfactant screening tests, bench-scale oxidation degradation studies (i.e., batch tests and one-dimensional column studies) are performed in the laboratory to investigate the reaction rates and mechanisms for the previously discussed oxidants using soils, NAPL (if available), and contaminated groundwater collected from the demonstration site. In the laboratory batch tests/kinetic studies, the samples are prepared in the reactor (e.g., 40 ml EPA vials) spiked with site contaminants (i.e., LNAPL and/or DNAPL) at the pre-determined concentrations (from high ug/L to low mg/L). These are the typical pollutant levels observed at the dilute plume area and/or after most NAPL mass has been removed from the contaminant source area. The Fenton's reagent and permanganate constituents, required to promote the respective oxidation reactions, are added to the reactor (e.g., 40 mL vials) at concentrations between 500 mg/L to ten percent. The samples are equilibrated for various reaction periods (from hours to days) at the demonstration site groundwater temperature. The final contaminant(s) and oxidant concentrations are measured. Changes of reaction parameters, such as pH and redox potential, Eh, are recorded. The reaction rate constants are calculated to quantify the removal of contaminant(s).

In addition, the demand for pH adjustment during chemical oxidation is evaluated, since many of the reactions involved are pH dependent. Maintaining the proper pH conditions for Fenton's oxidation is crucial to the availability of the ferrous ion (Fe²⁺) catalyst. The buffer capacity of the soil determines whether pH adjustment for chemical oxidation is effective and/or economical. To evaluate the effects of pH, testing is performed using potassium permanganate and Fenton's reagent under acidic, neutral, and basic conditions. Similar batch/kinetic tests for varying solution pH are conducted as previously described. Soil and groundwater conditions can affect chemical oxidation performance through direct competition with contaminants for the oxidant and should, therefore, be taken into account.

The primary interference with Fenton's oxidation is carbonate and bicarbonate, which influence pH conditions and compete with contaminants for the hydroxyl radical. Elevated soil organic matters react with Fenton's reagent and potassium permanganate. Oxidation of heavy metals, such as trivalent chromium (Cr(III)), remobilize the toxic form of metals like hexavalent chromium, Cr(VI), and therefore increase the unwanted risk at the site. If potential risk of remediation of Cr is present, additional tests are conducted to address these concerns depending on the selected site conditions (e.g. Cr desorption test in the soil peak columns). Typically, a phased approach is used to streamline the tests and minimize the number of tests. This can be achieved by evaluating the degradation rates of the targeted pollutant using the potential oxidants in a batch experiment. Only those oxidants with favorable degradation rates will be further investigated on their consumption rate with the site-specific soil. The chemical oxidant with minimum mass losses to the soil is thereafter tested in a one-dimensional column or a two-dimensional sand tank in order to optimize their conditions for complete degradation of pollutant in field. The optimal chemical oxidation system is thereafter able to be selected for the field application and is therefore site specific or site optimized.

EXAMPLE 1 Sequent Surfactant Flushing and Chemical Oxidation for LNAPL Remediation A Gasoline-Contaminated Underground Storage Tank (UST) Site

A particular gasoline contaminated-site is located in the southeastern Oklahoma town of Golden. The main contaminant is gasoline fuel as a result of the leakage of USTs from two former corner gas stations. Depth to the contaminated zone was 5 to 25-feet. Most free phase LNAPLs were trapped in the shallow zone (5 to 15 ft) containing sandy silt, silty clay, and silt. The treated area covered approximately 25,000 ft². The primary goal of the project was to remove all free phase gasoline. The secondary goal was to demonstrate a significant decrease in soil and groundwater concentrations (one to two orders of magnitude). The tertiary goal was to see how low the final contaminant concentration in groundwater could be achieved, to approach the Maximum Contaminant Level (MCL).

Before field implementation, Golden site LNAPL, and soil and groundwater samples were obtained and used to screen for the optimal surfactant systems. In the laboratory screening experiments, four anionic surfactant/co-surfactant mixtures were investigated for their potential use in remediating Golden LNAPL (fuel gasoline) with the in situ surfactant flushing technology disclosed and claimed herein. The selected surfactant/co-surfactant included mixtures of (1) sodium dioctylsulfosuccinate (AOT: 75% active. Aerosol OT 75% PG surfactant, by Cytec Industries, Inc., West Paterson, N.J., USA) and sodium dihexylsulfosuccinate (AMA), (2) AOT and polyoxyethylene sorbitan monooleate (Tween 80), (3) AOT and linear alkyl diphenyloxide disulfonate (Calfax 16 L—35% active, by Pilot Chemical Company, Santa Fe Springs, Calif., USA), and (4) Alkylamine sodium sulfonate (Lubrizol DP10052) and AMA. All surfactant solutions were prepared according to their percent activity. For example, a 100 g 0.75% AOT solution is prepared by adding 1 g of AOT raw material (75% active) to 99 g of H₂O (water). The laboratory screening activities consisted of numerous tests including surfactant-NAPL phase behaviors, surfactant sorption and precipitation, and contaminant extraction-column studies as described previously in the experiment methodology section (also see Shiau et. al., 1994; Shiau et. al. 1995; Shiau, et. al. 2000). As shown in Table 1, batch surfactant screening experiments indicate that all four surfactant mixtures used can achieve Winsor Type III (middle-phase) microemulsion with Golden site NAPL, mostly at total surfactant concentration less than 1 wt %.

TABLE 1 Summary of Surfactant/NAPL Phase Behaviors NAPL (TPH) solubility Equilibrated Surfactant at optimal Time of Stable Concentration Appearance of Type III Type III Evaluated Winsor Type III system Microemulsion¹ Surfactant System wt % Microemulsion mg/L (hr) AOT/AMA   1 to 2 transparent 440,000 1 to 2  AOT/Tween 80 0.2 to 1 translucent 400,000 8 to 12 AOT/Calfax16L-35² 0.2 to 1 translucent 450,000 1 to 2  Lubrizol DP/AMA³ 0.2 to 1 opaque 400,000 8 to 12 ¹NaCl (ranging from 0.1 to 3 wt %) was used to achieve the optimal Type I system at various ratios of surfactant mixtures ²Surfactant system used at Golden UST site ³A small portion of the contaminated zone was treated with this surfactant

Table IA illustrates the formulation of the preferred surfactant system AOT/Calfax 16 L—35 used at the Golden site for gasoline clean-up. Also surfactant formulations for other contaminants, such as diesel fuel and TCE, are also listed in Table IA.

TABLE IA Surfactant Co-surfactant Electrolyte Type of Contaminants wt % wt % wt % Microemulsion Gasoline Dioctylsulfosuccinate sodium linear NaCl Winsor Type III (AOT) alkyl diphenyloxide disulfonate (Calfax 16L-35) 0.75 0.19 1.2 Diesel Fuel dioctylsulfosuccinate sodium linear NaCl Winsor Type III (AOT) alkyl diphenyloxide disulfonate (Calfax 16L-35) 0.75 0.19 1.7 TCE Dioctylsulfosuccinate sodium linear NaCl Winsor Type III (AOT) alkyl diphenyloxide disulfonate (Calfax 16L-35) 0.77 0.27 1.84

The screening tests were conducted at different surfactant/co-surfactant ratios by adding various amounts of NaCl to promote the formation of a middle-phase (or Winsor Type III) microemulsion. In these tests, a low surfactant concentration (<1 wt %) approach was found to significantly improve the cost effectiveness of the site clean-up effort. Based on the screening tests, it was concluded that one surfactant system was the best candidate for the site-specific conditions (i.e., able to produce a translucent middle-phase microemulsion with ultra-low interfacial tension at value<0.005 dyne/cm and the highest NAPL solubility): a combination of anionic surfactant mixture, AOT/Calfax 16 L—35 (total concentration=0.94 wt %) at AOT/Calfax weight ratio (wt %/wt %) of 0.75/0.19 with 1.2 wt % NaCl added. The prepared formulation is shown in Table IA.

For the polishing step, abiotic chemical oxidation was used to treat the residual oil and dilute plume at the shallow zone of this site the Golden site. Both Fenton's Reagent and potassium permanganate were evaluated. As shown in Table 2, at a low concentration of chemical oxidant, Fenton's Reagent appeared to be more favorable in treating the BTEX compounds found at the site.

TABLE 2 Representative Results of BTEX Degradation with Fenton's Reagent m, p- Fenton's Benzene¹ % Toluene % Ethylbenzene % Xylene % o-Xylene % Reagent Used reduction reduction reduction reduction reduction H₂O₂ = 2,000 mg/L 92 44 59 47 44 Fe⁺² = 90 mg/L pH = 2 to 3 adjusted by 50% H₂SO₄ H₂O₂ = 2,000 mg/L 93 NA² NA NA NA Fe⁺² = 90 mg/L pH = 2 to 3 adjusted by 50% H₂SO₄ ² KMnO₄ = 5,000 mg/L³ 8 NA NA NA NA ¹Initial BTEX mixtures containing 1,000 ug/L of individual compound; reaction time = 12 hr ²Initial benzene-only concentration = 4,000 ug/L; NA = not available ³Initial benzene-only concentration = 1,000 ug/L

For example, 93% of the initial 4,000 μg/L benzene was degraded using a Fenton's Reagent, containing H₂O₂, 2,000 mg/L, Fe⁺², 90 mg/L, pH value@2 to 3. Benzene degradation was only 8% of the initial 1,000 μg/L benzene after a 5,000 mg/L KMnO₄ solution was added.

As shown in Table 3, one-dimensional column tests were conducted to assess the contaminant removal under hydrodynamic condition. Injection of a one pore volume of AOT/Calfax (0.94%) mixture was able to mobilize >90% of the trapped LNAPL from the 1-D column.

TABLE 3 Summary of 1-D Column Study Results Post- Post-surfactant surfactant + chem (Step 1) oxide (Step 2) Total % contaminant % contaminant contaminant Process Used removed removed removal % Step 1: 91¹ 8.6² 99.6² Surfactant: AOT/Calfax (0.94 wt %) + NaCl 1.2 wt % (1PV) Step 2: Fenton's Reagent: H₂O₂ (0.4 wt %) Fe⁺² (90 mg/L) pH = 2.6 ¹Estimated based on the mobilized NAPL volume and dissolved NAPL data; initial column oil saturation = 2% ²Based on final soil extraction measurement

Fenton's Reagent was selected to polish the residual NAPL after the surfactant flood. Representative column results are shown in FIG. 2 and Table 3. In the soil column, the total NAPL removed (measured by total petroleum hydrocarbon, TPH, or gasoline range organics, GRO) was 99.6%. Without the polishing step (chemical oxidation), the surfactant flushing alone could not achieve remediation to an extremely low contaminant level in the soil. Direct injection of a high concentration Fenton's Reagent (H₂O₂ level at 10 wt %) would have required multiple pore volumes (>5 PV) to achieve 80% to 90% contaminant removal (data not shown). Therefore, laboratory experiments indicated that integrated surfactant flushing followed by chemical oxidation would be able to treat the Golden site NAPL to extreme low level concentrations (low ppb range).

In situ surfactant flushing was used to recover free phase LNAPL (gasoline) using the low concentration surfactant (<1 wt %) and polishing oxidant methodology of the presently disclosed and claimed invention. One pore volume of 0.94 wt % AOT-Galfax16 L—35 (Table IA) surfactant (190,000 gallons) was injected into the contaminated shallow zone (source area, mostly silty material) over a two month period to mobilize the trapped NAPL. Initial free phase gasoline thickness on the water table ranged between 2.7 feet to 3.3 feet. Representative results from the field remediation effort at the Golden UST site are shown in FIGS. 3 and 4 and in Tables 4 and 5.

TABLE 4 Representative Contaminant Concentration in Golden Soil before and after the Sequent Surfactant Flushing and Chemical Oxidation Soil Sample Comparison Data Pre-Flush vs. Post Flush Calfax/AOT Flush TPH- Percent Percent Sample Depth Benzene Toluene Ethylbenzene Xylenes Gro Reduction Reduction Number ft. bgl. ug/kg ug/kg ug/kg Ug/kg mg/kg Benzene TPH-Gro MLS-1A 12.5 13400.0 58100.0 18800.0 92700.0 809.0 PTGP-2A 12.5 511.0 9970.0 3520.0 20600.0 164.0 96.2 79.7 MLS-1B 14.0 16000.0 185000.0 85300.0 454000.0 3630.0 PTGP-2B 14.0 2350.0 37300.0 14600.0 78600.0 548.0 85.3 84.9 MLS-2A 12.5 31800.0 438000.0 114000.0 595000.0 5080.0 GP-7A 12.5 2400.0 41800.0 17100.0 95700.0 691.0 PTGP-9A 12.5 225.0 476.0 ND ND 56.0 99.3 98.9 MLS-2B 14.0 4980.0 26700.0 6640.0 38100.0 345.0 PTGP-9B 14.0 284.0 ND 527.0 3790.0 59.0 94.3 82.9 DW-1A 11.0 1900.0 14900.0 8750.0 48400.0 355.0 PTGP-1A 11.0 ND ND ND ND 4.2 >99 98.8 DW-1B 14.0 11200.0 99800.0 44900.0 250000.0 2190.0 PTGP-1B 14.0 2670.0 4920.0 7580.0 28400.0 137.0 76.2 93.7 DW-5A¹ 14.0 20800.0 148000.0 58800.0 326000.0 2780.0 GP-6B 14.0 1210.0 12720.0 5820.0 31900.0 325.0 94.2 88.3 DW-8A 14.0 41100.0 182000.0 54600.0 277000.0 2560.0 PTGP-10A 14.0 1060.0 42700.0 19700.0 104000.0 890.0 97.4 65.2 DW-16A¹ 11.0 9720.0 277000.0 129000.0 707000.0 5740.0 PTGP-12A 11.0 ND 118.0 ND ND 19.0 >99 99.7 Notes: Background Concentration ¹The 14 foot sample for DW-5A and DW-16A denotes the 14 foot depth, unlike DW-1A.

TABLE 5 Oklahoma Corporation Commission (OCC)/U.S. Environmental Protection Agency (U.S. EPA) Post Test Soil Sample Results Concentration, mg/kg Sample Depth TPH- I.D. Ft. bgl. benzene Toluene ethylbenzene xylenes Gro PB-1 15.8 0.425 1.93 1.12 4.29 88.3 PB-2 16.7 0.103 0.170 0.035 0.190 1.83 PB-2 18.5 2.27 8.07 2.390 13.4 111.0 PB-3 17.7 0.295 3.02 1.20 6.87 54.5 PB-3 18.5 0.165 0.374 0.054 0.299 2.40 PB-4 17.0 4.24 16.7 4.14 21.6 155 PB-5 10.2 0.072 0.675 0.28 1.86 18.8 PB-5 17.3 0.727 6.31 2.18 13.1 160.0

No visible or instrumental evidence of free phase gasoline was detected in 25 recovery and monitoring wells (three out of 28 wells had minimal thicknesses) during the post surfactant sampling event (FIG. 3). The observed benzene concentration indicated that 75%-99% reduction in soil concentrations were achieved during the surfactant flush (FIG. 4 and Table 4). Similarly, a reduction of TPH (GRO) concentrations in the soils was between 65%-99%. After surfactant flushing, the remaining trace residual and dissolved NAPL were treated by the final polishing steps using chemical oxidation in the shallow zone, where most NAPL was present before the surfactant flushing. Representative soil concentrations after the post-oxidation phase are summarized in Table 5. As shown in Tables 4 and 5, further contaminant reduction/degradation (OCC/EPA soil sampling event held in June, 2002) was observed after the post-polishing step was completed. These results indicate that the integrated surfactant flushing and chemical oxidation methodology of the presently disclosed and claimed invention is capable of remediating contaminants to substantially non-detected or extremely low level, if not completely removed, in a “real world” field-scale test.

EXAMPLE 2 Sequent Surfactant Flushing and Chemical Oxidation Polishing for DNAPL A TCE-Contaminated Site

The targeted site was contaminated by TCE, a DNAPL and common degreaser. The main focus of this experiment was to treat the dilute TCE plume with an in-situ chemical oxidation process. This approach was selected rather than treating the source zone NAPL because the DNAPL source zones could not be identified. Most laboratory efforts were focused on evaluating the effectiveness of two selected oxidants, potassium permanganate (KmnO₄) and Fenton's reagent, for TCE and cis-DCE degradation. A limited effort was given to evaluate the effectiveness of sequent surfactant flushing and chemical oxidation to treat the TCE-contaminated source (or hot) zone.

Use of Potassium Permanganate for TCE/DCE Degradation

Batch experiments were conducted to evaluate the degradation rates of TCE, cis-DCE, or their mixture by KMnO₄. These experiments were carried out in TCE/DCE dissolved solutions in the absence (Table 6) or presence (Table 7) of site-specific soil. As shown in Table 6, 250 mg/L KMnO₄ can degrade TCE or DCE completely at low contaminant levels. Initial contaminant concentrations ranged from several hundred of ug/L to more than 100 mg/L. As shown in Table 7, KMnO₄ concentrations ranging from 10 mg/L up to 10,000 mg/L (1%) solution were tested. Results indicated that most reactions between KMnO₄ and TCE, DCE, and TCE/DCE mixtures (between few hundreds ppb to 5 ppm) were complete after a 24-hr reaction period.

TABLE 6 Degradation Reaction of KMnO₄ and low level of TCE, DCE and their mixtures without soil Final KMnO4 TCE Final DCE added, TCE, DCE Sample ID ug/L ug/L mg/L % degraded % degraded DCE-C-8 8 4820 0 NA 0 (control) DCE-100-8 3 691 100 NA 85.7 DCE-250-8 0 22 250 NA 99.5 TCE-C-8 283 0 0 0 NA (control) TCE-100-8 0 1 100 100 NA TCE-250-8 0 1 250 100 NA D&T-C-8 70 1407 0 0 0 (control) D&T-100-8 0 14 100 100 99.0 D&T-250-8 0 11 250 100 99.2 Note: -8 samples were analyzed after 29 hrs of sample preparation.

TABLE 7 Degradation Reaction of KMnO₄ and TCE, DCE and their mixtures with two types of soil (Soil 1-26′-27′; Soil 2-18′-20′, in 40 mL solution) Final KMnO₄ TCE Final DCE added TCE % DCE Sample ug/L ug/L mg/L degraded % degraded SDCE-C 18 5486 0 NA 0 SDCE-100 0 17 100 NA 99.7 SDCE-250 0 16 250 NA 99.7 STCE-C 237 0 0 0 NA STCE-100 0 0 100 100 NA STCE-250 0 0 250 100 NA ST&D-C 117 2432 0 0 0 ST&D-100 0 13 100 100 99.5 ST&D-250 0 12 250 100 99.5

Most reactions between KMnO₄ and TCE/DCE are completed in less than one hour under room temperature (20° C.). As shown in Table 8, experiments conducted with soil added indicate that complete degradation of TCE and DCE was observed under similar conditions.

TABLE 8 Degradation Reaction of KMnO₄ and high level of TCE without soil Initial KMnO₄ Final TCE added TCE Sample ID mg/L mg/L % degraded Control 343 0.0 0 T10000 0.0 10,000 100 T5000 0.0 5,000 100 T1000 0.0 1,000 100 T500 111 500 67.7

The loss of KMnO₄ in two soil samples collected from the site were determined to be negligible during 4-, 7-, and 14-days of reaction period (data not shown). Low sorption loss of KMnO₄ reduced the amount of KMnO₄ required and the total cost of remediation project.

Under higher initial TCE levels (>300 mg/L), results indicate that adding 1,000 mg/L or more KMnO₄ completely degraded the added TCE. A 67.7% reduction of TCE was observed with 500 mg/L of KMnO₄ solution.

Batch study indicated that addition of potassium permanganate degraded dissolved TCE and DCE in the dilute plume near the vicinity of the soil sampling locations. In addition, other loss mechanisms for permanganate including sorption and fortuitous reactions with other reduced compounds were minimal in the tested samples.

Use of Fenton's Reagent for TCE/DCE Degradation.

Fenton's reagent is the second oxidant tested. Fenton's reagent was prepared by dissolving H₂O₂ and catalysis Fe(II) (FeCl₂ or FeSO₄) in acidic solution (HCl or H₂SO₄).

Batch results indicated that Fenton's reagent degrades both TCE and DCE, but appears less efficient compared to KMnO₄ on a weight basis. For example, 283 ug/L TCE can be completely degraded by 100 mg/L KMnO₄ solution, yet 100 mg/L H₂O₂/FeCl₂ solution only oxidize 51.7% of TCE. For similar contaminant concentrations, DCE degradation required more Fenton's reagent than TCE. Note that some pollutants, such as trichloroethane (TCA) or BTEX, could not be completely degraded by KMnO4, but will be degraded effectively by Fenton's reagent.

The batch studies clearly indicate that both KMnO₄ and Fenton's reagent were candidates for degrading the target contaminant, TCE, and the common intermediate, DCE, at the selected sampling locations at the DNAPL-impacted site.

1-D Column Study with KMnO₄-Only for TCE Removal.

Several column tests were conducted by injecting KMnO₄ at different concentrations (100, 500, 5000, 20000 mg/L) under various TCE residual saturation in the soil packed column. In the column study, fifteen to twenty five pore volumes of KMnO₄ were injected to evaluate the removal of TCE under the hydrodynamic conditions.

At a 1% initial TCE residual saturation, significant gas bubbles (mainly CO₂ gas) were observed in the effluent after a 5,000-mg/L KMnO₄ solution was injected, while TCE concentration also began to drop significantly (to less than 10 mg/L level). In another column test, a 10% TCE residual saturation was used with various KMnO₄ levels being injected (100, 500, 5,000, 20,000 mg/L). Similarly, numerous gas bubbles were created when higher KMnO₄ concentrations were injected (5,000 mg/L and above) (data not shown). In addition, dark brown MnO₂ precipitates were accumulated at various locations in the column.

After the KMnO₄ flushing, the treated column was dismantled and the soil was extracted with methanol to determine the final TCE concentration. The final TCE concentrations in the column ranged from 8 mg/Kg to 47 mg/Kg in different columns (both low and high initial TCE levels). A significant amount of TCE was degraded with KMnO₄ flushing. However, a significant release of CO₂ near the NAPL source area could potentially change the hydraulic permeability of the aquifer and lead to by-pass around the TCE ganglia preventing further removal, as other researchers have suggested. In addition, significant accumulation of MnO₂ precipitates at the interface of NAPL and water also reduce the mass transfer of KMnO₄ to TCE and decrease the TCE degradation rate. This problem has been observed in field trials with KMnO₄ and is a limitation of the technology for remediation of a contaminated hot zone. Results from these column tests indicate that injection of KMnO₄ alone could effectively degrade TCE under proper conditions, such as for a TCE-impacted dissolved plume but not in areas with free phase DNAPL or high level of TCE residual saturation. Chemical oxidation is very effective for degrading a TCE dilute plume or as a polishing-step for source zone remediation after the majority of the TCE is removed by the surfactant flooding. The relatively low quantity of remaining TCE would be less likely to cause manganese precipitation and hydraulic bypassing upon reaction with KMnO₄.

1-D Column Study with Sequent Surfactant Flushing and Chemical Oxidation (KMnO₄) Flushing for TCE Removal.

Additional column tests were conducted using surfactant flushing to first remove significant TCE NAPL mass, followed by KMnO₄ flushing to degrade the TCE left in the column. Examples of the column study results are shown in FIG. 5. Initial TCE residual saturation was 2%. At 4 PV, a surfactant solution, containing 2.5% dihexyl sulfosuccinate (AMA), 5% diphenyl oxide disulfonate (Calfax), 3% NaCl, and 1% CaCl₂, was injected into the column. The selection of this surfactant system was based on a previous field test done for a mixed DNAPL contaminated site, containing tricholorethane (TCA), TCE, DCA, and DEC. The enhancement of TCA solubility with the selected surfactant system (Calfax/AMA/CaCl₂/NaCl) is listed in Table 9.

TABLE 9 Comparison of Trichloroethane (TCA) Solubilization in Batch and Column Studies Maximum TCA TCA Solubilized in Solubilized in column Surfactant System Batch test (mg/L)¹ test (mg/L) Dowfax/AMA/NaCl/CaCl₂ 99,259 168,996 Lubrizol71/IPA/NaCl/ 259,355 NA³ CaCl₂ ¹Volume determined by volumetric addition of TCA during the phase behavior study ²Surfactant used in the sequent surfactant flushing/chemical oxidation test ³NA = not available

A surfactant system used for TCA could be used for TCE (with similar hydrophobicity property) to produce a middle-phase microemulsion. Therefore, a mixture of Calfax/AMA surfactant was used to conduct this 1-D column test. Significant TCE mass (concentration reached 100,000 mg/L) was removed from the column after surfactant breakthrough. After 5 PV of surfactant flushing, a 2,000 mg/L KMnO₄ solution was injected to further degrade the TCE in the column. A total of 4 PV of KMnO₄ solution was injected in the column before post-water flushing began at 12 PV injection time.

Significant TCE mass was removed during the surfactant flushing period. A decrease of the TCE concentration, eventually below the quantification limit, after the KMnO₄ breakthrough, is also clearly demonstrated. Post column extraction indicated that 99.94% of the initial TCE was removed from the column. Note that the surfactant concentration used in this column test was 7.5 wt %. As shown in Table 10, a recent batch study conducted by Applicant indicates that a low surfactant concentration (<1 wt %) could achieve similar solubility enhancement for TCE.

TABLE 10 Solubilization of DNAPL (TCE) Using Low Surfactant Concentration (1 wt %) Sample TCE Solubilized in Note Name Phase bacth test mg/L 1 wt % surfactant fb-015s middle 177104 Calfax/AOT fb-015s aqueous 99577 Calfax/AOT fb-014s middle 383813 Calfax/AOT fb-014s aqueous 66677 Calfax/AOT fb-008 aqueous 152882 Lubrizol System

Therefore, a surfactant flushing with a low surfactant concentration system (e.g., Calfax/AOT—see Table IA for TCE) followed by a chemical oxidation step significantly improves the state of the art and makes it technologically and economically viable to completely remediate contaminated sites.

Complex Viscous Non-Aqueous Phase Liquids.

An additional embodiment of the currently disclosed and claimed invention pertains to a surfactant flushing system that is capable of remediating soil and groundwater that has been contaminated by or impacted by complex viscous NAPLs. Injection of a selected biodegradable co-solvents at predetermined volumes prior to injecting a pre-selected surfactant (as described hereinabove) significantly enhances the performance of such a surfactant flushing step for recovering highly viscous oils or NAPLs. Suitable biodegradable co-solvents for use in the presently disclosed and claimed invention include, without limitation, the oil derivatives from natural/engineered agriculture edible fats and oily products, such as soybean oil, canola oil, citrus, grape oil, vegetable oils as well as combinations or derivations thereof.

Examples of suitable biodegradable co-solvents include methyl and ethyl esters of fatty acids. Two particular examples are SoyGold® 2000 (CAS No. 67784-80-9, AG. Environmental Products, Lenexa, Kans., U.S.A) and SoyGold® 1000 (CAS No. 67784-80-9) (similar to SoyGold® 2000 but with no surfactant added). The SoyGold® 2000 co-solvent is a fatty acid methyl esters, with alkyl chain C16-C18, or methyl esters of soybean oil. An amount of the biodegradable co-solvent may also include trace amounts of one or more surfactants in order to increase the biodegradable co-solvent's dispersivity in the water. For viscous fluids (i.e. those fluids having a viscosity between 50 cp to 1500 cp or higher), in one embodiment the alkyl chain is a C12-C24 chain having a viscosity range of between 1 to 20 cp for easy delivery and enhanced injectivity in the subsurface.

One of the considerations for successful delivery of the biodegradable co-solvent in the subsurface is that any such biodegradable co-solvent should be miscible in water. Therefore, in addition to the good biodegradability, the dispersivity of these co-solvents in water should be carefully evaluated before field implementation. Without good dispersivity in water, the injected co-solvent might separate into different phases in the soil and dramatically reduce their effectiveness on oil recovery. Another example of the biodegradable co-solvent for the presently claimed and disclosed invention is d'Limonene (CAS No. 5989-27-5, Florida Chemical Company, Inc., Winter Haven, Fla.). The d-Limonene is the major component of the oil extracted from citrus rind. Additional co-solvents may be considered for the environmental clean-up application but less environmentally desirable may include naphtha, mineral spirit, mid to long chain alcohols (>C5) and other petroleum-based solvents.

For remediation of complex viscous oils impacted soil and groundwater, pre-injection of 0.02 to 0.5 pore volume (PV) of the selected biodegradable co-solvent, documented in the presently claimed and disclosed invention enhances the effectiveness of the surfactant system for mobilization of the trapped oil as described previously in U.S. Pat. No. 6,913,419 and U.S. Pat. No. 7,021,863, entitled “In situ surfactant and chemical oxidant flushing for complete remediation of contaminants and methods of using the same”, the specification which is hereby expressly incorporated in its entirety herein by reference. Addition of biodegradable co-solvent before surfactant injection may have multiple purposes, including decreasing the viscosity of the target contaminants, promoting the desorption of the trapped oils from the soil, and likely improving sweep efficiency in conjunction with the surfactant (and the polymer) flushing.

The ideal surfactant system may be selected based on their capability to form the middle phase microemulsions (or achieving ultra-low interfacial tention) between the target contaminant and the surfactant as described in detail previously in U.S. Pat. No. 6,913,419 and U.S. Pat. No. 7,021,863, entitled “In situ surfactant and chemical oxidant flushing for complete remediation of contaminants and methods of using the same”, the specification which is hereby expressly incorporated in its entirety herein by reference. One example is a mixture of doctylsulfosuccinate (AOT) and sodium linear alkyl diphenyloxide disulfonate (Calfax 16 L—35) with surfactant concentration, listed previously in U.S. Pat. No. 6,913,419 and U.S. Pat. No. 7,021,863, entitled “In situ surfactant and chemical oxidant flushing for complete remediation of contaminants and methods of using the same”, the specification which is hereby expressly incorporated in its entirety herein by reference, would produce the middle phase microemulsions for a variety of complex viscous oils, including coal tars, heating oils, creosote and others as described previously in U.S. Pat. No. 6,913,419 and U.S. Pat. No. 7,021,863, entitled “In situ surfactant and chemical oxidant flushing for complete remediation of contaminants and methods of using the same”, the specification which is hereby expressly incorporated in its entirety herein by reference. The target pore volume (PV) for the surfactant flushing (or surfactant injection) which followed the co-solvent injection may be between 1 to 5 PV. In general, a combination of surfactant solution and a selected polymer solution may be injected simultaneously to improve the sweep of the flushing on NAPL removed. After the surfactant flushing, a freshwater, or recycled treated water from the recovered fluid may be used to further mobilize the released complex viscous NAPL until most NAPL have been captured and recovered. This post-surfactant water flushing may last one to three pore volumes. Thus, by combining the co-solvent pre-injection and surfactant with a polymer drive and post-water flushing as described in this invention, significant amounts of complex viscous oil (likely greater than 90% of initial trapped oil) could be removed from the subject site. After majority of the NAPL been removed, one can then use chemical oxidant injection as described in prior invention to further treat the dilute plume to achieve the clean-up levels and close the site.

One advantage of this invention is that no (or minimum) addition of heat or thermal energy is required to achieve the goal of removing the complex viscous oils. This is a significant improvement on the project cost and design of the equipment for the above-ground water treatment system. Another benefit of this invention is that the biodegradable co-solvent left in the soil and groundwater after completion of the project may be easily degraded by the native microorganisms under the site-specific conditions. In addition, these viscous oils may be trapped under the existing building or in a deeper subsurface zone (>30 ft depth below ground surface, bgs), in situ surfactant flushing with help from pre-injection of biodegradable co-solvents may be one of the very few technologies which can access the contaminants without digging a significant amount of site soil before removing the contaminants.

EXAMPLE 3

A viscous coal tar sample (a dense non-aqueous phase liquid DNAPL) was retrieved from a contaminated site located in northeast part of U.S.A. The site-specific coal tar DNAPL viscosity is close to 40 cp at 20° C. (63 cp at 15° C.) measured in this study. The site-specific DNAPL, soil, and groundwater samples were obtained and used to screen for the optimal surfactant system(s). In the laboratory screening experiments, a mixture of anionic sulfosuccinate (AOT or so called DOSS-70)/dialkyl disulfonated diphenyl oxide (Calfax—16 L)/NaCl surfactants were investigated for their potential use in remediation of the DNAPL with the in situ surfactant flushing technology. The phase behavior study indicated a mixture of 0.75 wt % AOT, 0.19 wt % dialkyl disulfonated diphenyl oxides surfactant and 1.7 wt % NaCl solution (previous patented surfactant formulation) may achieve the optimal middle phase microemulsion for this DNAPL. Therefore, this surfactant system was selected for further one-dimensional (1-D) column study to evaluate the coal tar oil removal efficacy in the sand-packed columns (see Table 1). As common practice, a polymer solution was used to enhance the mobility control of the mobilized viscous oil. In addition to surfactant flushing-alone, a combination of pre-flushing biodegradable co-solvent (0.25 PV) and injection of the selected surfactant system was assessed to evaluate the enhancement of biodegradable co-solvent on the performance of oil removal in the soil.

TABLE 11 Summary of Selected Column Test Results Parameter Column #2 Column #4 Column #6 Surfactant used 1.25 PV, 0.75 wt % 2 PV, 0.75% AOT 2 PV, 0.75% AOT (or AOT (or DOSS)/ (or DOSS)/0.19 wt % DOSS)/0.19 wt % 0.19% Calfax/1.7 wt % Calfax/1.7 wt % Calfax/1.7 wt % NaCl NaCl NaCl with (Pre-flushed with pH adjusted by 0.25 PV co-solvent NaOH (~40 mg/L) SoyGold ® 2000 - to 11 97% active) Polymer drive 1.25PV, 1200 mg/L 2 PV, 1500 mg/L 2 PV, 1500 mg/L AP-1120 (dissolved FLOPAAM 3630 FLOPAAM 3630 (co- and co-injected (co-injected w/ injected w/ with surfactant) surfactant) surfactant) Post flush 1 PV tap water 3 PV tap water 3 PV tap water free product 6.2 ml (initial 6.2 ml (initial 6.2 ml (initial added added added in to column added in)-20% in)-20% initial free product final packed with North initial residual residual saturation Shore site clean saturation 0.1 ml left (5.3 ml soil)-20% initial 0.9 ml left (5.3 ml collected) NAPL residual collected) saturation* 1.2 ml left (4 ml collected) Total NAPL 64.5% 85%* 98.5%* removed (%) *Site contaminated soil contained 8,600 mg/kg diesel range organics measured by GC/FID (less than the 20% residual saturation used in the 1-D column study) **Soil used in Column 2, 4 & 6: combined soil samples with hot air dried, passed through No. 12 sieve (= 1.68 mm)

As determined from these laboratory results, significant free product NAPL (>95%) can be effectively removed (via mobilization) in a 1-D column packed with sieved fine sand material retrieved from the subject site using the developed pre-co-solvent and low surfactant and polymer flushing without adding the heat. The optimal surfactant system was able to remove 64.5-85% of NAPL from the sand-packed column. Addition of bio-degradable co-solvent with the surfactant flushing would further improve the recovery of these complex viscous fluids. Therefore, the invention of this process could save the remediation project cost and the actual time frame for remediating the complex viscous fluids.

EXAMPLE 4

The second NAPL was a weathered No. 6 heating oil retrieved from a site located in northeastern state of U.S. The heating oil was trapped under the current building and required the remedial approach to remove the free phase NAPL without impacting the routine activity of the building. A series of surfactant screening tests were conducted to select the optimal surfactant system to mobilize the viscous oil. The site NAPL viscosity was more than 1,000 cp at 20° C. measured in this study. The resulting surfactant-NAPL phase behavior studies are summarized in Table 2. This table shows that the low interfacial tension of these systems indicate the applicability of the selected surfactant system for mobilization of this viscous heating oil. The observed middle phase (or Winsor Type III) microemulsion volume was negligible likely due to high viscosity of this NAPL (data not shown). The IFT measurement of NAPL and surfactant solution indicated the optimal surfactant system occurs with 2.1% NaCl added. Therefore, this dual surfactant system (0.75 wt % AOT (or DOSS)/0.19 wt % Calfax/2.1 wt % NaCl) was selected for further investigation in a one-dimensional column test. Removal of LNAPL will be mainly controlled by mobilization mechanism with this surfactant system.

TABLE 12 Composition of surfactants and interfacial tension measurements of the equilibrated phase Interfacial Surfactant Tension, IFT* Sample # Salinity (% NaCl) Dyne/cm A1 1.0 0.017 B1 1.3 0.034 C1 1.5 0.032 D1 1.9 0.021 E1 2.1 0.0073 F1 2.3 0.0077 *The formulations (0.75 wt % AOT/0.19 wt % Calfax in Sample# A1-F1 as described previously in U.S. Pat. No. 6,913,41, entitled “In situ surfactant and chemical oxidant flushing for complete remediation of contaminants and methods of using the same”, the specification which is hereby expressly incorporated in its entirety herein by reference) form negligible middle phases microemulsion (phase transition from Winsor Type Ito Type II directly). The optimal surfactant system contains 2.1% NaCl determined by the IFT measurement.

Typically, recovery of viscous free product NAPL may require addition of a polymer (preferably non-toxic or low toxic compounds) dissolved in the surfactant solution to increase the sweep efficiency of the mobilized oil during the chemical flood. Under most conditions, addition of the selected polymer at low concentration levels of 500 mg/L to 2000 mg/L to enhance the performance of oil recovery may not pose any negative impact on the NAPL/surfactant microemulsion behavior. In addition, the material safety data sheets of the selected surfactants and polymers (all non-toxic) and the bio-degradable co-solvents used in the site-specific laboratory treatability studies should be provided to the Federal and/or State regulatory agencies before proceeding with the field implementation tasks.

The optimal AOT/Calfax/NaCl surfactant system was investigated in the one-dimensional column study. Two non-toxic polymer systems, AP-1120 and FLOPAAM 3630, were selected for increasing the viscosity of the surfactant solution. These polymers are anionic water-soluble polymers used as flocculant in water treatment plant (AP-1120) and/or for enhanced oil recovery (FLOPAAM 3630). The material safety data sheets for these surfactants and polymers are readily available for further consideration of their applicability and injection into the subsurface. Initial column tests indicated that several challenges were met for mobilization of this viscous NAPL. The selected liquid chromatograph pump could not pump the site NAPL easily. Therefore, the subject site soil was pre-treated with site LNAPL to achieve 20% residual saturation-impacted soil before packing into 1-D column. Use of surfactant/polymer flushing produced negligible NAPL removal (<10%) after 3 PV surfactant injection (data not shown in the Table 3). Additional column tests were conducted to evaluate enhanced NAPL recovery by adding short chain alcohol (pentanol) or increase of temperature (50° C.), yet no significant improvement was observed in these efforts (data not shown in the table).

Further column tests indicated that injection of the biodegradable co-solvent SoyGold 2000® (between 0.25 PV to 2 PV were injected) to pre-flush the site NAPL (viscosity>1000 cp@20° C.) in the sand-packed column could dramatically increase the NAPL removal with the selected surfactant/polymer flush (greater than 90% NAPL removal). The selected SoyGold 2000® for this study is nontoxic and easily biodegraded in the soil based on the product information. Representative results of Columns No. 6 & 7 are summarized in Table 3. Results show that the recovery of No. 6 heating oil NAPL using an integrated co-solvent pre-flush (0.25 PV) and the surfactant/polymer flush was greater than 95%, as compared to less than 10% NAPL removal with the surfactant/polymer-only flush. Therefore, pre-flushing the selected biodegradable co-solvent, such as methyl esters of soybean oil along with the patented low surfactant system (AOT/Calfax) and polymer flush may provide significant advantages for site remediation of highly viscous oil, such as the weathered No. 6 heating oil found at this contaminated site. It should be noted that a trace amount of SoyGold 2000® (close to 750 mg/Kg soil based on the DROs analysis and the resulted chromatogram) was detected in the treated soil after the pre-co-solvent and the surfactant/polymer flush. It is believed that this residual co-solvent will be easily biodegraded in the soil in reasonable time frame or can be degraded by injection of low chemical oxidant as a post-flushing polishing step (such as Fenton's Reagent) to reach non-detected level, if necessary. After a few weeks, the co-solvent left in the columns #6 and #7 was below the non-detectable level, likely due to the biodegradation of oil under aerobic conditions. Typically, the oil degradation under anaerobic condition would take a longer time frame to achieve a similar oil degradation. Based on the results of this study, one could anticipate the residual co-solvent in the soil, after the flushing, to be degraded in one to a few months under anaerobic conditions.

Another advantage of injection bio-degradable co-solvent as listed in this finding is the amount of co-solvent injected. We find only 0.02 to 0.5 PV of bio-degradable co-solvent may be required to achieve significant oil removal. Use of the common co-solvents, such as short chain alcohol (butanol, iso-butanol, and pentanol) may require at least one to several pore volumes (PV) injection before seeing significant improvement of surfactant flushing and/or co-solvent-alone flushing. Minimizing the dosage of bio-degradable co-solvent may dramatically reduce the costs of above-ground treatment (and chemical use) to separate the recovered NAPL and the co-solvent before recycling/reuse the recovered fluid and the final disposal of the recovered waste fluid and the contaminants.

TABLE 13 Summary of Selected Column Test Results Parameter Column #6 Column #7 Co-solvent 1 PV, 97% SoyGold ® 0.25 PV, 97% SoyGold ® pre-flush 2000 2000 Surfactant used 3 PV, 0.75 wt % 3 PV, 0.75 wt % AOT/ AOT/0.19 wt % Calfax/ 0.19 wt % Calfax/2.1 wt % 2.1 wt % NaCl NaCl Polymer drive 3 PV, 1500 mg/L 3 PV, 1500 mg/L FLOPAAM FLOPAAM 3630 (co- 3630 (co-injected w/ injected w/ surfactant) surfactant) Post flush 3 PV tap water 3 PV tap water Initial NAPL 31,235 mg/Kg TPH* 14,484 mg/Kg TPH concentration Final NAPL 1,161 mg/Kg TPH 709 mg/Kg TPH concentration Total NAPL 96.3%* 95.1%* removed (%) *TPH (diesel range organics) were measured by GC/FID with methylene chloride extraction. **Soil used in Columns #6 & #7: site soil sample was pre-washed with acetone, and hot air dried @ 200° C., and then was passed through No. 12 sieve (= 1.68 mm) before use; column tests were conducted @ 20° C.

It is anticipated that a polymer drive (using the selected polymers, either AP-1120 or FLOPAAM 3630) is required to have better sweep efficiency, as described herein. The added polymer (at concentration between 500 mg/L to 2000 mg/L) was dissolved in the surfactant solution and co-injected with the selected surfactant. In a separate study, more than 90% of viscous No. 2 heating oil was removed by adding the polymer in surfactant solution compared to 10 to 20% NAPL removal with surfactant-only system under similar conditions. Without better mobility control, the surfactant injected may generate a so-called “fingering” phenomenon that results in physical bypassing of the trapped NAPL phase. Polymer addition, for better mobility control, was commonly used in the enhanced-oil recovery. Therefore, an integrated pre-co-solvent and surfactant/polymer flush is suitable for removal of the complex viscous oils found at various contaminated sites based on the results of these studies.

Although the present invention has been described in considerable detail with reference to certain preferred versions thereof, other versions are possible. For example, single surfactant systems such as anionic/anionic and nonionic/nonionic mixtures; surfactant systems such as anionic/cationic and anionic/nonionic mixtures; and contaminants such as polyaromatic hydrocarbons (PAH), coal tars, creosote, crude oil, pesticides, polychorinated biphenyls (PCBs) and ketones can be utilized with this integrated approach. Therefore, the spirit and scope of the appended claims should not be limited to the description of the preferred versions contained herein. In addition, further cost savings and process improvements can be realized by recycling the recovered bio-degradable co-solvent. In this group, ongoing research and development are focusing on optimizing the recycling/reuse processes to treat the recovered fluids, including mixtures of bio-degradable co-solvent and the recovered viscous NAPLs. After treatment, the recycled/reused bio-degradable co-solvent can be re-injected to the untreated and/or treated contamination zone to further remove the targeted contaminants.

REFERENCES

The following references, to the extent that they provide exemplary procedural or other details supplementary to those set forth herein, are specifically incorporated herein by reference in their entirety as though set forth herein in particular.

-   Abdul, A. S., Gibson, T. L., Ang, C. C., Smith, J. C.,     Sobezynski, R. E., 1992. “In situ surfactant washing of     polychlorinated biphenyls and oils from a contaminated site.” Ground     Water, 30:219-231. -   Abdul, A. S., Ang, C. C., 1994. “In situ surfactant washing of     polychlorinated biphenyls and oils from a contaminated field site:     phase II pilot study. Ground Water, 32:727-734. -   Brown, C. L., Delshad, M., Dwarakanath, Jackson, R. E.,     Londergan, J. T., Meinardus, H. W., McKinney, D. C., Oolman, T.,     Pope, G. A., and Wade, W. H., 1999, Demonstration of surfactant     flooding of an alluvial aquifer contaminated with dense nonaqueous     phase liquid.” in Innovative Subsurface Remediation, Field Testing     of Physical, Chemical, and Characterization Technologies,     Brusseau, M. L., Sabatini, D. A., Gierke, J. S., Annable, M. D.     (eds.), ACS symposium series 725, 64-85, American Chemical Society,     Washington D.C. -   Cayias, J. L., Schechter, R. S., and Wade, W. H., 1975. “The     measurement of low interfacial tension via the spinning drop     technique. In Adsorption at Interfaces, ACS Symposium Series No. 8,     Amer. Chem. Soc., Washington, D.C., pp. 234-247. -   Fountain, J. C., Starr, R. C., Middleton, T. Beikirch, M., Taylor,     C., and Hodge, D., 1996. “A controlled field test of     surfactant-enhanced aquifer remediation,” Ground Water, 34(5):910. -   Haber, F., and Weiss, J. 1934. The catalytic decomposition of     hydrogen peroxide by iron salts. Proceedings of the Royal Society of     London, Series A, v. 147, p. 332-351. -   Jawitz, J. W., Annable, M., Rao, P. S. C., and Rhue, R. D., 1998.     “Field implementation of Winsor Type I surfactant/alcohol mixture     for in situ remediation of a complex LNAPL as a single phase     microemulsion,” Environ. Sci. and Technol., 32 (4): 523-530. -   Knox, R. C., Sabatini, D. A., Harwell, J. H., Brown, R. E., West, C.     C., Blaha, and Griffin, C. 1997. “Surfactant remediation field     demonstration using a vertical circulation well,” Ground Water.     35(6): 948-953. -   Knox, R. C., Shiau, B. J., Sabatini, D. A., and Harwell, J.     H., 1999. “Field demonstration studies of surfactant-enhanced     solubilization and mobilization at Hill Air Force Base, Utah,” in     Innovative Subsurface Remediation, Field Testing of Physical,     Chemical, and Characterization Technologies, Brusseau, M. L.,     Sabatini, D. A., Gierke, J. S., Annable, M. D. (eds.), ACS symposium     series 725, 49-63, American Chemical Society, Washington D.C. -   Lipe, M., Sabatini, D. A., Hasegawa, M., and Harwell, J. H. 1996.     Ground Water Monitering and Remediation. 16(1): 85-92. -   Martel, R., Gelinas, P. J. and Desnoyyers, J. E., “Aquifer washing     by micellar solutions: 1 Optimization of alcohol-surfactant-solvent     solutions,” J. Contaminant Hydrology. 1998a. 29(4): 317. -   Martel, R., Rene, L, and Gelinas, P. J., 1998b. “Aquifer washing by     micellar solutions: 2. DNAPL recovery mechanisms for an optimized     alcohol-surfactant-solvent solution,” J. Contaminant Hydrology.     30(1-2): 1. -   Pennell, K. D., Jin, M., Abriola, L. M., Pope, G. A., 1994.     “Surfactant-enhanced remediation of soil columns contaminated by     residual tetrachloroethylene, J. Contaminant Hydrology. 16: 35-53. -   Pennell, K. D., Pope, G. A., Abriol, L. M., 1996. “Influence of     viscous and buoyancy forces on the mobilization of residual     tetrachloroethylene during surfactant flushing. Environ. Sci.     Technol. 30: 1328-1335. -   Reitsma, S. and Marshall, M, 2002, “Experimental Study of Oxidation     of Pooled NAPL,” in Chemical Oxidation and Reactive Barriers:     Remediation of Chlorinated and Recalcitrant Compounds, The Second     International Conference on Remediation of Chlorinated and     Recalcitrant Compounds. eds. G. B. Wickramanayake, A. R.     Gavaskar, A. S. C. Chen, Battelle Press, Columbus, Ohio, pp. 25-32. -   Rouse, J. D., Sabatini, D. A., Harwell, J. H., 1993, Environmental     Science & Technology, 27: 2072 -   Sabatini, D. A., Harwell, J. H., and Knox, R. C., 1998a. “Surfactant     selection criteria for enhanced subsurface remediation: Laboratory     and field observations.” Progr. Colloid Polym Sci. 111: 168-173. -   Sabatini, D. A., Harwell, J. H., Hasegawa, M., and Knox, R. C.,     1998b. “Membrane processes and surfactant-enhanced subsurface     remediation: results of a field demonstration,” Journal of Membrane     Science, 151: 87-98. -   Shiau, B. J., Sabatini, D. A., Harwell, J. H., 1994, Ground Water,     32: 561. -   Shiau, B. J., Sabatini, D. A., Harwell, J. H., 1995, Environmental     Science & Technology, 29: 2929. -   Shiau, B. J., Sabatini, D. A., Harwell, J. H., 2000, “Chlorinated     solvent removal using food grade surfactants: column studies,” J. of     Environmental Engineering, 126(7): 611. -   Shiau, B. J., Hasegawa, M. A., Brammer, J. M., Carter, T.,     Goodspeed, M., Harwell, J. H., Sabatini, D. A., Knox, R. C.,     Szekeres, E., 2002. “Field demonstration of surfactant-enhanced     DNAPL remediation: two case studies,” in Chlorinated Solvent and     DNAPL Remediation. Innovative Strategies for Subsurface Cleanup,     Henry, S. M., Warner, S. D. (eds.), ACS symposium series 837, 51-72,     American Chemical Society, Washington D.C. 

1. A method for substantially removing subsurface contaminants, comprising the steps of: introducing via in-situ injection an effective amount of at least one pre-selected surfactant solution to a targeted treatment zone, wherein the effective amount of at least one pre-selected surfactant solution is a mixture of sodium diocytisulfosuccinate and linear alkyl diphenyloxide disulfonate; and introducing via in-situ injection an effective amount of at least one pre-selected biodegradable co-solvent to the targeted treatment zone, wherein the effective amount of the at least one pre-selected biodegradable co-solvent in combination with the effective amount of the at least one pre-selected surfactant solution remove subsurface contaminants to substantially undetectable or extremely low levels.
 2. The method of claim 1, wherein the effective amount of at least one pre-selected biodegradable co-solvent is introduced first and the effective amount of the at least one pre-selected surfactant solution is introduced second.
 3. The method of claim 1, further comprising the step of: introducing via in-situ injection an effective amount of at least one pre-selected chemical oxidant to the targeted treatment zone, wherein the at least one pre-selected chemical oxidant degrades any remaining subsurface contaminants to substantially undetectable or extremely low levels.
 4. The method of claim 1, wherein the effective amount of at least one pre-selected surfactant solution is from about 0.05 weight % to about 15.0 weight %.
 5. The method of claim 1, wherein the effective amount of at least one pre-selected surfactant solution is from about 3.0 weight % to about 8.0 weight %.
 6. The method of claim 1, wherein the effective amount of at least one pre-selected surfactant solution is from about 1.0 weight % to about 3.0 weight %.
 7. The method of claim 1, wherein the effective amount of at least one pre-selected surfactant solution is from about 0.05 weight % to about 1.0 weight %.
 8. The method of claim 2, wherein the amount of at least one biodegradable co-solvent introduced before the at least one pre-selected surfactant solution is about 0.02 pore volumes to about 0.5 pore volumes.
 9. The method of claim 3, wherein the effective amount of at least one pre-selected chemical oxidant is selected from the group consisting of hydrogen peroxide, potassium permanganate and combinations thereof.
 10. The method of claim 3, wherein at least one pre-selected chemical oxidant is a free radical.
 11. The method of claim 1, wherein the effective amount of at least one bio-degradable co-solvent is selected from the group consisting of methyl esters of fatty acids, ethyl esters of fatty acids and combinations thereof.
 12. A method for substantially removing subsurface contaminants, comprising the steps of: introducing via in-situ injection an effective amount of at least one pre-selected surfactant solution to a targeted treatment zone, wherein the effective amount of at least one pre-selected surfactant solution is a mixture of alkylamine sodium sulfonate and sodium dihexylsulfosuccinate; and introducing via in-situ injection an effective amount of at least one pre-selected biodegradable co-solvent to the targeted treatment zone, wherein the effective amount of the at least one pre-selected biodegradable co-solvent in combination with the effective amount of the at least one pre-selected surfactant solution remove subsurface contaminants to substantially undetectable or extremely low levels.
 13. The method of claim 12, wherein the effective amount of at least one pre-selected biodegradable co-solvent is introduced first and the effective amount of the at least one pre-selected surfactant solution is introduced second.
 14. The method of claim 12, further comprising the step of: introducing via in-situ injection an effective amount of at least one pre-selected chemical oxidant to the targeted treatment zone, wherein the at least one pre-selected chemical oxidant degrades any remaining subsurface contaminants to substantially undetectable or extremely low levels.
 15. The method of claim 12, wherein the effective amount of at least one pre-selected surfactant solution is from about 0.05 weight % to about 15.0 weight %.
 16. The method of claim 12, wherein the effective amount of at least one pre-selected surfactant solution is from about 3.0 weight % to about 8.0 weight %.
 17. The method of claim 12, wherein the effective amount of at least one pre-selected surfactant solution is from about 1.0 weight % to about 3.0 weight %.
 18. The method of claim 12, wherein the effective amount of at least one pre-selected surfactant solution is from about 0.05 weight % to about 1.0 weight %.
 19. The method of claim 13, wherein the amount of at least one biodegradable co-solvent introduced before the at least one pre-selected surfactant solution is about 0.02 pore volumes to about 0.5 pore volumes.
 20. The method of claim 14, wherein the effective amount of at least one pre-selected chemical oxidant is selected from the group consisting of hydrogen peroxide, potassium permanganate and combinations thereof.
 21. The method of claim 14, wherein at least one pre-selected chemical oxidant is a free radical.
 22. The method of claim 12, wherein the effective amount of at least one bio-degradable co-solvent is selected from the group consisting of methyl esters of fatty acids, ethyl esters of fatty acids and combinations thereof.
 23. A method for substantially expediting subsurface remediation of contaminants, comprising the steps of: introducing via in-situ injection an effective amount of at least one bio-degradable co-solvent first to a targeted treatment zone; introducing via in-situ injection and effective amount of at least one surfactant solution to a targeted treatment zone, wherein that effective amount of at least one surfactant solution is a mixture of sodium diocytlsulfosuccinate and linear alkyl diphenyloxide disulfonate, and further wherein the effective amount of at least one surfactant solution remediates at least one subsurface contaminant; and introducing via in-situ injection an effective amount of at least one pre-selected chemical oxidant to a targeted treatment zone.
 24. The method of claim 23, wherein at least one subsurface contaminant is a dense non-aqueous phase liquid.
 25. The method of claim 23, wherein at least one subsurface contaminant is a light non-aqueous liquid.
 26. The method of claim 23, wherein the effective amount of at least one bio-degradable co-solvent is selected from the group consisting of methyl esters of fatty acids, ethyl esters of fatty acids and combinations thereof.
 27. A method for substantially expediting subsurface remediation of contaminants, comprising the steps of: introducing via in-situ injection an effective amount of at least one bio-degradable co-solvent first to a targeted treatment zone; introducing via in-situ injection and effective amount of at least one surfactant solution to a targeted treatment zone, wherein that effective amount of at least one surfactant solution is a mixture of alkylamine sodium sulfonate and sodium dihexylsulfosuccinate, and further wherein the effective amount of at least one surfactant solution remediates at least one subsurface contaminant; and introducing via in-situ injection an effective amount of at least one pre-selected chemical oxidant to a targeted treatment zone.
 28. The method of claim 27, wherein at least one subsurface contaminant is a dense non-aqueous phase liquid.
 29. The method of claim 27, wherein at least one subsurface contaminant is a light non-aqueous liquid.
 30. The method of claim 27, wherein the effective amount of at least one bio-degradable co-solvent is selected from the group consisting of methyl esters of fatty acids, ethyl esters of fatty acids and combinations thereof. 